CN109137116B

CN109137116B - Preparation method of collagen fiber containing carbon nano tube

Info

Publication number: CN109137116B
Application number: CN201810742697.8A
Authority: CN
Inventors: 丁长坤; 杜建华; 程博闻; 曹悦苗; 岳程飞; 李璐
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2018-07-09
Filing date: 2018-07-09
Publication date: 2020-03-10
Anticipated expiration: 2038-07-09
Also published as: CN109137116A

Abstract

The invention discloses a preparation method of collagen fiber containing carbon nano-tubes, which comprises the step of spinning a spinning solution containing carbon nano-tubes and collagen; the carbon nano tube is a multi-wall carbon nano tube, the length of the carbon nano tube is 0.5-2 mu m, and the diameter of the carbon nano tube is 8-15 nm; the weight ratio of the carbon nano tube to the collagen is 1: 35-60. The present invention can obtain collagen fibers having further improved breaking strength.

Description

Preparation method of collagen fiber containing carbon nano tube

Technical Field

The invention relates to a preparation method of collagen fiber containing carbon nano tubes, in particular to a preparation method of regenerated collagen fiber containing carbon nano tubes.

Background

The carbon nano tube has excellent mechanical, electrical and optical properties. The carbon nano-tube is easy to agglomerate, and especially the extremely strong hydrophobicity of the carbon nano-tube cannot achieve stable homogeneous dispersion in a water system. In order to improve the dispersion properties of carbon nanotubes, there are generally covalent bond modifications and non-covalent bond modifications. The covalent bond modified carbon nano tube is grafted with carboxyl or amino groups and other groups on the surface, and the carbon nano tube shows biological toxicity. Non-covalently modified (e.g., surfactant modified) carbon nanotubes can penetrate cells, but do not exhibit significant biological toxicity. CN106521676A discloses a preparation method of high-performance polyethylene fiber and carbon nanotube composite fiber: adding the carbon nano tube into concentrated sulfuric acid, adding potassium permanganate for reflux reaction, cooling, and then adding concentrated hydrochloric acid to obtain a purified carbon nano tube; adding the carbon nano tube into ethanol for ultrasonic treatment, heating under high-speed magnetic stirring, adding isopropanol, filtering, drying, and performing Soxhlet extraction to obtain a functionalized carbon nano tube; preparing a high-performance polyethylene fiber solution, adding carbon nano tubes and an antioxidant, performing ultrasonic treatment and heating to prepare a high-performance polyethylene fiber and carbon nano tube gel solution; adding the gel precursor into a double-screw spinning machine for spinning to obtain gel precursor, and extracting, drying and stretching to obtain the high-performance polyethylene fiber and carbon nano tube composite fiber. The composite fiber is poor in biodegradability because polyethylene is used as a matrix.

Collagen is the most abundant protein in animal connective tissues, accounts for about 20-30% of the total amount of animal body protein, and has good biodegradability, the distribution of collagen in animal bodies has specificity, for example, type I collagen mainly exists in animal body tendon, and accounts for about 90% of the total amount of animal body collagen, type I collagen molecules are composed of three α peptide chains, and have a triple helix conformation, the diameter is about 1.5nm, and the length is about 300nm, so that the collagen has excellent biocompatibility, low antigenicity, degradability and the like due to the special triple helix structure.

CN103007357A discloses a method for preparing a carbon nanotube/collagen-based composite material, wherein the content of carbon nanotubes is 0.2-4.0%, and the material can be formed into porous sponge and gel materials, but cannot be spun into fibers. CN107158394A discloses a method for preparing collagen-coated carbon nanotubes, which cannot be spun into fibers. CN105887236A discloses a heat-storage artificial wig fiber containing peacock feather, which takes polyacrylonitrile and collagen as spinning dope, and the added nano bamboo charcoal powder and carbon nano tubes can provide the fiber with the effects of heat storage, heat preservation, humidity regulation and the like. The above method requires addition of a synthetic polymer such as polyacrylonitrile to obtain fibers, and thus has poor biodegradability.

In view of the above, it is desirable to develop a method for preparing a collagen fiber containing carbon nanotubes without adding a synthetic polymer.

Disclosure of Invention

The invention discovers that collagen fibers with improved mechanical properties can be obtained by adding specific carbon nanotubes into collagen. The present invention aims to provide a method for producing a collagen fiber containing carbon nanotubes, which further improves the breaking strength. The invention achieves the above purpose through the following technical scheme.

A preparation method of collagen fiber containing carbon nano-tube comprises the steps of spinning a spinning solution containing carbon nano-tube and collagen; wherein the carbon nano tube is a multi-wall carbon nano tube, the length of the carbon nano tube is 0.5-2 mu m, and the diameter of the carbon nano tube is 8-15 nm; the weight ratio of the carbon nano tube to the collagen is 1: 35-60.

According to the preparation method of the invention, the weight ratio of the carbon nanotubes to the collagen is preferably 1: 50-55.

According to the preparation method of the present invention, preferably, the carbon nanotubes are carbon nanotubes modified by a cationic surfactant; the cationic surfactant is C9-C25 alkyl trimethyl ammonium halide.

According to the preparation method of the invention, preferably, the C9-C25 alkyl trimethyl ammonium halide is selected from cetyl trimethyl ammonium bromide or dodecyl trimethyl ammonium chloride; the weight ratio of the cationic surfactant to the carbon nano tube is 1: 3-10.

According to the preparation method of the present invention, preferably, the collagen is regenerated collagen derived from rat tail, cow hide or pig skin.

The preparation method according to the present invention preferably comprises the steps of:

(1) preparing the surfactant modified carbon nano tube: adding a carbon nano tube into an aqueous solution containing a cationic surfactant, carrying out ultrasonic treatment at the temperature of 20-27 ℃ for 1-3 h, then centrifuging at the rpm of 5000-12000 for 10-30 min, and removing precipitates; dialyzing the obtained clear liquid by using a dialysis bag with the molecular weight cutoff of 7000-10000, and changing water once every 3-6 h for 3-9 times to obtain a dispersion liquid;

(2) preparing a spinning solution: adding acetic acid into the dispersion until the concentration of the acetic acid is 0.35-0.55 mM; adding collagen sponge fragments, swelling for 10-30 min, stirring for 3-6 h to dissolve to a homogeneous phase, performing centrifugal deaeration for 30-60 min at 0-10 ℃, and performing cold storage curing for 15-36 h to obtain a spinning stock solution;

(3) spinning: transferring the spinning solution into an injection pump, placing a spinning nozzle of the injection pump above the liquid level of a coagulation bath for 6-10 mm, extruding the spinning solution, enabling the obtained spinning trickle to fall into the coagulation bath, precipitating while coagulating, taking out after 1-5 min, hanging at 20-27 ℃, applying 3-9 g of gravity to the lower end of the spinning trickle for drafting, and completely drying to obtain a precursor;

(4) and (3) crosslinking: dipping the protofilament in an absolute ethyl alcohol solution containing glutaraldehyde for 5-15 min, then taking out, naturally hanging, applying 10-15 g of gravity drawing at the lower end, and completely drying to obtain the collagen fiber containing the carbon nano tube.

According to the preparation method of the present invention, preferably, in the step (1), the concentration of the cationic surfactant in the aqueous solution of the cationic surfactant is 0.16 to 0.64 wt%, and the concentration of the carbon nanotube is 0.08 to 0.16 wt%; the dialysis bag is a dialysis bag with the molecular weight cutoff of 8000-9000.

According to the preparation method of the present invention, preferably, in the step (2), the collagen concentration in the spinning solution is 3 to 5 wt%.

According to the preparation method of the invention, preferably, in the step (3), the extrusion speed is 0.3-1.0 ml/min; the coagulating bath is formed by acetone, ammonia water and deionized water in a volume ratio of 100: 6-7: 1-3.

According to the preparation method provided by the invention, preferably, in the step (4), the dipping temperature is 28-35 ℃; the absolute ethanol solution containing glutaraldehyde contains 0.3-0.8 wt% of glutaraldehyde, and has a pH of 7.5-8.5.

The invention adds a certain amount of specific carbon nano tubes into collagen, thereby obtaining the collagen fiber with improved mechanical property. The spinning solution of the invention does not need to add synthetic polymer, thus having better biodegradability. In addition, by controlling the process parameters, the method of the invention can further improve the breaking strength of the collagen fibers.

Detailed Description

The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.

The collagen fibers of the present invention are fibers whose matrix is formed of collagen, and thus do not contain a synthetic polymer. The collagen fiber of the present invention contains carbon nanotubes and may contain other fillers. The preparation method of the collagen fiber containing the carbon nano tube comprises the step of spinning the spinning solution containing the carbon nano tube and the collagen. In the spinning dope, the carbon nanotubes and the collagen are uniformly dispersed. The fiber formed by spinning takes collagen as a matrix, and the carbon nano tubes are dispersed in the matrix. The carbon nanotube of the present invention is a multiwalled carbon nanotube, has a length of 0.5 to 2 μm, and has a diameter of 8 to 15 nm. Preferably, the length is 0.6 to 1.5 μm and the diameter is 9 to 13 nm. More preferably, the length is 0.7 to 1 μm and the diameter is 10 to 12 nm. The collagen fiber with improved mechanical property can be obtained by adding the carbon nano tube into collagen. The carbon nanotubes are too long, which results in a reduction in the breaking strength of the fibers; too short a length of the carbon nanotube causes deterioration of its dispersibility and an increase in cost. Too large a diameter of the carbon nanotube will result in a reduction in the breaking strength of the fiber; too short a length of the carbon nanotube causes deterioration of dispersibility thereof, increase of cost, and decrease of breaking strength of the fiber. In the spinning solution, the weight ratio of the carbon nano tube to the collagen is 1: 35-60; preferably 1: 38-58; more preferably 1:50 to 55. Carbon nanotubes outside the above range result in a decrease in the breaking strength of the fiber.

In the present invention, the carbon nanotube may be a carbon nanotube modified with a cationic surfactant. After modification, the compatibility of the carbon nano tube and the collagen is increased, thereby being beneficial to improving the breaking strength of the fiber. The cationic surfactant of the present invention may be a C9-C25 alkyltrimethylammonium halide, preferably a C12-C18 alkyltrimethylammonium halide. Examples of C9 to C25 alkyl groups include, but are not limited to, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, or the like. Examples of ammonium halides include, but are not limited to, ammonium bromide, ammonium chloride, and the like.

According to one embodiment of the invention, the C9-C25 alkyltrimethylammonium halide is selected from cetyltrimethylammonium bromide or dodecyltrimethylammonium chloride; preferably hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide). The weight ratio of the cationic surfactant to the carbon nano tube can be 1: 3-10; preferably 1: 4-8. Thus being beneficial to improving the compatibility of the carbon nano tube and the collagen and having small influence on the strength of the fiber matrix.

In the present invention, the collagen may be regenerated collagen. The collagen can be derived from rat tail, cow hide or pig skin. Preferably, the collagen is regenerated collagen derived from rat tail, cow hide or pig skin; more preferably, regenerated collagen type I. This is advantageous in ensuring the strength of the collagen fibers.

The preparation method comprises the following steps: (1) preparing a surfactant modified carbon nano tube; (2) preparing a spinning solution; (3) spinning; (4) and (3) a crosslinking step.

In the step (1), adding the carbon nano tube into an aqueous solution containing a cationic surfactant, carrying out ultrasonic treatment at the temperature of 20-27 ℃ for 1-3 h, then centrifuging at the rpm of 5000-12000 for 10-30 min, and removing precipitates; and dialyzing the obtained clear liquid by using a dialysis bag with the molecular weight cutoff of 7000-10000, and changing water every 3-6 hours for 3-9 times to obtain the dispersion liquid. According to one embodiment of the present invention, the concentration of the cationic surfactant in the aqueous solution of the cationic surfactant is 0.16 to 0.64 wt%, and the concentration of the carbon nanotubes is 0.08 to 0.16 wt%; the dialysis bag is a dialysis bag with the molecular weight cutoff of 8000-9000.

In step (1), the kind of the cationic surfactant is as described above. The concentration of the cationic surfactant in the aqueous solution of the cationic surfactant may be 0.16 to 0.64 wt%, preferably 0.32 to 0.5 wt%. The concentration of the carbon nanotubes may be 0.08 to 0.16 wt%, preferably 0.08 to 0.12 wt%. This facilitates dispersion of the carbon nanotubes.

In the step (1), the ultrasonic treatment temperature can be 20-27 ℃, and is preferably 23-25 ℃; the ultrasonic treatment time can be 1-3 h, preferably 2-2.5 h. The rotation speed of the centrifugal treatment can be 5000-12000 rpm, preferably 8000-10000 rpm, such as 9000 rpm; the centrifugal treatment time may be 10 to 30min, preferably 15 to 25 min. After centrifugation, the precipitate was removed. And dialyzing the obtained clear liquid by using a dialysis bag with the cut-off molecular weight of 7000-10000 Da, preferably 8000-9000 Da. In the dialysis process, water is changed every 3-6 h, preferably 3-5 h; changing the water for 3-9 times, preferably 5-7 times. And (2) preparing a spinning solution from the dispersion liquid obtained in the step (1).

In the step (2), adding acetic acid into the dispersion until the concentration of the acetic acid is 0.35-0.55 mM; and adding collagen sponge fragments, swelling for 10-30 min, stirring for 3-6 h to dissolve to a homogeneous phase, performing centrifugal deaeration for 30-60 min at 0-10 ℃, and performing cold storage curing for 15-36 h to obtain a spinning stock solution. According to an embodiment of the present invention, the collagen concentration in the spinning dope is 3 to 5 wt%.

In the step (2), the concentration of acetic acid may be 0.35 to 0.55mM, preferably 0.38 to 0.8 mM. mM means mmol/L. The collagen sponge fragments are raw materials for regenerating collagen. Swelling the collagen sponge fragments in the dispersion liquid for 10-30 min, preferably 15-20 min; and then stirring for 3-6 h, preferably 4-5 h, dissolving the collagen sponge fragments and forming a homogeneous solution. And (4) centrifuging and defoaming the homogeneous solution, refrigerating and curing to obtain the spinning solution. The temperature of centrifugal deaeration is 0-10 ℃, and preferably 3-8 ℃; the time for centrifugal defoaming is 30-60 min, preferably 35-50 min. This ensures sufficient deaeration, thereby improving spinnability. The cold-storage ripening can be carried out in a refrigerator or freezer. The temperature for refrigerating and curing can be 0-10 ℃, and preferably 3-8 ℃; the time for cold storage curing is 15-36 h, preferably 20-25 h. And (4) forming a spinning solution after refrigeration and curing for the spinning step.

And (3) transferring the spinning stock solution into an injection pump, placing a spinning nozzle of the injection pump above the liquid level of a coagulation bath for 6-10 mm, extruding the spinning stock solution, allowing the obtained spinning trickle to fall into the coagulation bath while coagulating, sinking for 1-5 min, taking out, suspending at 20-27 ℃, applying 3-9 g of gravity to the lower end of the spinning trickle for drafting, and completely drying to obtain the precursor. According to the preparation method, the extrusion speed is preferably 0.3-1.0 ml/min; the coagulating bath is formed by acetone, ammonia water and deionized water in a volume ratio of 100: 6-7: 1-3. The conditions are adopted, so that the breaking strength of the collagen is improved.

In the step (3), the spinneret keeps a proper distance from the liquid level of the coagulating bath, so as to be beneficial to fiber forming. The spinneret may be located 6 to 10mm, preferably 7 to 9mm, above the liquid level of the coagulation bath. The dope is extruded from the spinneret to form a fine stream of spun yarn, which falls into a coagulation bath. The extrusion rate may be 0.3 to 1.0ml/min, preferably 0.5 to 0.8 ml/min. The coagulating bath can be formed by acetone, ammonia water and deionized water in a volume ratio of 100: 6-7: 1-3; for example, the water-based paint is formed by acetone, ammonia water and deionized water in a volume ratio of 100: 6.5-7: 1-1.5. Gradually solidifying the spinning trickle, keeping the spinning trickle in a solidification bath for 1-5 min, preferably 2-3 min, and then fishing out; and then dried. The drying temperature can be 20-27 ℃, and is preferably 23-25 ℃; the drying time is not particularly limited as long as it is completely dried. In the drying process, the fibers fished out from the coagulating bath are hung, and the lower end of the fibers is subjected to gravity drawing of 3-9 g, preferably 5-7 g. A weight such as a weight may be used to apply gravity. And (4) carrying out crosslinking treatment on the dried protofilament.

In the step (4), dipping the protofilament in an absolute ethyl alcohol solution containing glutaraldehyde for 5-15 min, then taking out, naturally hanging, applying 10-15 g of gravity to the lower end for drafting, and completely drying to obtain the collagen fiber containing the carbon nano tube. The dipping temperature can be 28-35 ℃, preferably 30-33 ℃, and the time can be 5-15 min, preferably 10-13 min. The impregnation liquid adopts absolute ethyl alcohol solution containing glutaraldehyde, wherein the glutaraldehyde is contained by 0.3-0.8 wt%, and preferably 0.5-0.6 wt%. The pH of the impregnation liquid is 7.5 to 8.5, preferably 7.6 to 8. According to one embodiment of the invention, the dipping temperature is 28-35 ℃; the absolute ethanol solution containing glutaraldehyde contains 0.3-0.8 wt% of glutaraldehyde, and has a pH of 7.5-8.5.

In step (4), the fiber is taken out after the impregnation is completed and dried. In the drying process, the fiber needs to be hung naturally, and the lower end of the fiber needs to be subjected to gravity drawing of 10-15 g, preferably 10-13 g. A weight such as a weight may be used to apply gravity. And drying to obtain the collagen fiber containing the carbon nano tube.

The collagen fiber containing the carbon nano tube mainly comprises collagen and the carbon nano tube; wherein the collagen accounts for 97.0-98.8 wt%, and the carbon nano tube accounts for 1.2-3.0 wt%; the carbon nanotube is a multi-walled carbon nanotube, has a length of 0.5 to 2 μm and a diameter of 8 to 15 nm. Preferably, the collagen accounts for 97.5-98.3 wt%, and the carbon nano tube accounts for 1.7-2.5 wt%. The collagen can be regenerated collagen from rat tail, cow leather or pig skin; for example, rat tail type I regenerated collagen, cow hide type I regenerated collagen, or pig skin type I regenerated collagen. The breaking strength of the collagen fiber containing the carbon nano tube is 2.19cN/dtex, preferably 2.25cN/dtex, even 2.31 cN/dtex.

The mechanical properties of the fibers were determined by the following methods: the mechanical properties of the fibers are tested by adopting a LLY-06 type electronic single fiber strength tester of Laizhou electronic instruments Limited, the clamping distance is 20mm, the stretching speed is 10mm/min, the dry test temperature is 25 ℃, and the relative humidity is 75%. Ten groups of data were measured separately and averaged.

Example 1

0.08 wt% of multi-walled carbon nano-tube (the length is 0.5-2 μm, the diameter is 8-15 nm) is added into an aqueous solution containing 0.32 wt% of Cetyl Trimethyl Ammonium Bromide (CTAB), ultrasonic treatment is carried out for 2h at the temperature of 25 ℃, centrifugation is carried out for 15min at 9000rpm, and precipitates are removed. Dialyzing with dialysis bag with molecular weight cutoff of 8000, changing water every 4 hr for 7 times to obtain stable dispersion.

Adding acetic acid into the dispersion until the concentration of the acetic acid is 0.5mM, adding 4 wt% of shredded collagen sponge, swelling for 15min, starting mechanical stirring for 4h, and dissolving to be homogeneous; and then transferring the fiber to a centrifuge tube, centrifuging and defoaming at low temperature of 4 ℃ for 40min, and aging in a refrigerator for 24h to obtain the spinning solution.

And (3) preparing a coagulating bath with the volume ratio of acetone, ammonia water and deionized water being 100:7:1 in a vertical coagulating bath with the height being more than 230 mm. The dope was transferred to a syringe pump, and the spinneret of the syringe pump was placed 8mm above the liquid surface of the coagulation bath. Extruding the spinning solution at an extrusion speed of 0.5ml/min, allowing the obtained spinning stream to fall into a coagulation bath while coagulating, taking out after 2min, suspending at room temperature, applying a weight of 5g to the lower end for drafting, and completely drying to obtain the precursor.

Adding 0.5 wt% of glutaraldehyde into absolute ethyl alcohol, and dropwise adding ammonia water to adjust the pH to 8, thereby obtaining absolute ethyl alcohol solution containing glutaraldehyde. Dipping the protofilament in absolute ethyl alcohol solution containing glutaraldehyde for 10min, and controlling the dipping temperature to be 30 ℃. And naturally hanging the dipped protofilaments, applying a weight of 10g to the lower end of the protofilaments, and completely drying to obtain the collagen fiber containing the carbon nano tube. The mechanical properties of the fibers are shown in Table 1.

Comparative example 1

0.04 wt% of multi-walled carbon nanotubes (5-30 μm in length and 1-2 nm in diameter) are added into an aqueous solution containing 0.32 wt% of cetyltrimethylammonium bromide (CTAB), and the mixture is subjected to ultrasonic treatment at 25 ℃ for 2h and centrifugation at 9000rpm for 15min to remove precipitates. Dialyzing with dialysis bag with molecular weight cutoff of 8000, changing water every 4 hr for 7 times to obtain stable dispersion.

And (3) preparing a coagulating bath with the volume ratio of acetone, ammonia water and deionized water being 100:7:1 in a vertical coagulating bath with the height being more than 230 mm. The dope was transferred to a syringe pump, and the spinneret of the syringe pump was placed 10mm above the liquid surface of the coagulation bath. Extruding the spinning solution at an extrusion speed of 0.5ml/min, allowing the obtained spinning stream to fall into a coagulation bath while coagulating, taking out after 2min, suspending at room temperature, applying a weight of 5g to the lower end for drafting, and completely drying to obtain the precursor.

Comparative example 2

0.08 wt% of multi-walled carbon nano-tube (the length is 0.5-2 μm, the diameter is 30-50 nm) is added into an aqueous solution containing 0.32 wt% of Cetyl Trimethyl Ammonium Bromide (CTAB), ultrasonic treatment is carried out for 2h at the temperature of 25 ℃, centrifugation is carried out for 15min at 9000rpm, and precipitates are removed. Dialyzing with dialysis bag with molecular weight cutoff of 8000, changing water every 4 hr for 7 times to obtain stable dispersion.

Comparative example 3

0.08 wt% of multi-walled carbon nanotubes (the length is 50 μm, the diameter is 8-15 nm) are added into an aqueous solution containing 0.32 wt% of cetyltrimethylammonium bromide (CTAB), ultrasonic treatment is carried out at 25 ℃ for 2h, centrifugation is carried out at 9000rpm for 15min, and precipitates are removed. Dialyzing with dialysis bag with molecular weight cutoff of 8000, changing water every 4 hr for 7 times to obtain stable dispersion.

Comparative example 4

Adding 0.5mM acetic acid into 4 wt% of shredded collagen sponge, swelling for 15min, starting mechanical stirring for 4h, and dissolving to homogeneous phase; and then transferring the fiber to a centrifuge tube, centrifuging and defoaming at low temperature of 4 ℃ for 40min, and aging in a refrigerator for 24h to obtain the spinning solution.

Adding 0.5 wt% of glutaraldehyde into absolute ethyl alcohol, and dropwise adding ammonia water to adjust the pH to 8, thereby obtaining absolute ethyl alcohol solution containing glutaraldehyde. Dipping the protofilament in absolute ethyl alcohol solution containing glutaraldehyde for 10min, and controlling the dipping temperature to be 30 ℃. The impregnated protofilament was hung naturally, and a weight of 10g was applied to the lower end of the protofilament, followed by complete drying to obtain collagen fibers. The mechanical properties of the fibers are shown in Table 1.

TABLE 1 spinning Process parameters and mechanical Properties of the fibers

The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims

1. A preparation method of collagen fiber containing carbon nano-tubes is characterized by comprising the following steps:

2. The method according to claim 1, wherein in the step (1), the concentration of the cationic surfactant in the aqueous solution of the cationic surfactant is 0.16 to 0.64 wt%, and the concentration of the carbon nanotubes is 0.08 to 0.16 wt%; the dialysis bag is a dialysis bag with the molecular weight cutoff of 8000-9000.

3. The method according to claim 1, wherein the concentration of collagen in the spinning dope in the step (2) is 3 to 5 wt%.

4. The method according to claim 1, wherein in the step (3), the extrusion rate is 0.3 to 1.0 ml/min; the coagulating bath is formed by acetone, ammonia water and deionized water in a volume ratio of 100: 6-7: 1-3.

5. The preparation method according to claim 1, wherein in the step (4), the dipping temperature is 28-35 ℃; the absolute ethanol solution containing glutaraldehyde contains 0.3-0.8 wt% of glutaraldehyde, and has a pH of 7.5-8.5.

6. The method according to claim 1, wherein the carbon nanotubes are multiwalled carbon nanotubes having a length of 0.5 to 2 μm and a diameter of 8 to 15 nm.

7. The method according to claim 1, wherein the carbon nanotube-containing collagen fiber is mainly composed of collagen and carbon nanotubes; wherein the collagen accounts for 97.0-98.8 wt%, and the carbon nano tube accounts for 1.2-3.0 wt%.

8. The method according to claim 1, wherein the cationic surfactant is a C9-C25 alkyltrimethylammonium halide.

9. The method of claim 8, wherein the C9-C25 alkyltrimethylammonium halide is cetyl trimethylammonium bromide or dodecyl trimethylammonium chloride.

10. The method according to claim 8, wherein the weight ratio of the cationic surfactant to the carbon nanotubes is 1:3 to 10.